Abstract: | Semirigid organic ligands can adopt different conformations to construct coordination polymers with more diverse structures when compared to those constructed from rigid ligands. A new asymmetric semirigid organic ligand, 4‐{2‐(pyridin‐3‐yl)methyl]‐2H‐tetrazol‐5‐yl}pyridine ( L ), has been prepared and used to synthesize three bimetallic macrocyclic complexes and one coordination polymer, namely, bis(μ‐4‐{2‐(pyridin‐3‐yl)methyl]‐2H‐tetrazol‐5‐yl}pyridine)bisdichloridozinc(II)] dichloromethane disolvate, Zn2Cl4(C12H10N6)2]·2CH2Cl2, ( I ), the analogous chloroform monosolvate, Zn2Cl4(C12H10N6)2]·CHCl3, ( II ), bis(μ‐4‐{2‐(pyridin‐3‐yl)methyl]‐2H‐tetrazol‐5‐yl}pyridine)bisdiiodidozinc(II)] dichloromethane disolvate, Zn2I4(C12H10N6)2]·2CH2Cl2, ( III ), and catena‐polydiiodidozinc(II)]‐μ‐4‐{2‐(pyridin‐3‐yl)methyl]‐2H‐tetrazol‐5‐yl}pyridine] chloroform monosolvate], {ZnI2(C12H10N6)]·CHCl3}n, ( IV ), by solution reaction with ZnX2 (X = Cl and I) in a CH2Cl2/CH3OH or CHCl3/CH3OH mixed solvent system at room temperature. Complex ( I ) is isomorphic with complex ( III ) and has a bimetallic ring possessing similar coordination environments for both of the ZnII cations. Although complex ( II ) also contains a bimetallic ring, the two ZnII cations have different coordination environments. Under the influence of the I? anion and guest CHCl3 molecule, complex ( IV ) displays a significantly different structure with respect to complexes ( I )–( III ). C—H…Cl and C—H…N hydrogen bonds, and π–π stacking or C—Cl…π interactions exist in complexes ( I )–( IV ), and these weak interactions play an important role in the three‐dimensional structures of ( I )–( IV ) in the solid state. In addition, the fluorescence properties of L and complexes ( I )–( IV ) were investigated. |